WO2017209281A1

WO2017209281A1 - Gold sputtering target

Info

Publication number: WO2017209281A1
Application number: PCT/JP2017/020617
Authority: WO
Inventors: 加藤　哲也; 陽平水野; 千春石倉
Original assignee: 田中貴金属工業株式会社
Priority date: 2016-06-02
Filing date: 2017-06-02
Publication date: 2017-12-07
Also published as: KR20210103593A; KR102614205B1; JP7077225B2; JP2022048244A; JP7320639B2; TW201742942A; US11817299B2; US20230126513A1; RU2018146163A3; US11569074B2; CN109196137A; US20190103257A1; JPWO2017209281A1; KR20190015346A; TWI752035B; EP3467141A1; CN109196137B; EP3467141A4; RU2018146163A; EP3467141B1

Abstract

Provided is a gold sputtering target that makes increased uniformity of Au film thickness distribution possible. This gold sputtering target is made of gold and unavoidable impurities and has a surface to be sputtered. In said gold sputtering target, the average Vickers hardness value is 40 to 60 and the average crystal grain diameter is 15 µm to 200 µm. In the surface to be sputtered, {110} planes of the gold are preferentially oriented.

Description

Gold sputtering target

The present invention relates to a gold sputtering target.

Au films deposited using a gold (Au) sputtering target are used in various fields because of the excellent chemical stability and electrical properties of Au itself. For example, in a quartz oscillator device, an Au sputtering film is used as an excitation electrode or the like formed on both sides of a quartz chip. In a quartz oscillator device, an Au sputtering target capable of forming an Au film with a uniform film thickness distribution at the time of sputtering is required because the vibration frequency is adjusted by the film thickness of the Au film.

With regard to the shape of the sputtering target, a plate-like sputtering target such as a disk or a rectangular plate used for planar magnetron sputtering is generally known. Apart from this, cylindrical sputtering targets are also known. The utilization rate of the target material at the time of sputtering is improved compared to a plate-like sputtering target, so that the cylindrical sputtering target begins to be developed with a ceramic material target, etc., and is also expanded to metal / alloy-based targets. Application is also underway, and application to noble metal targets such as silver (Ag) is also being studied (see Patent Documents 1 and 2).

Also in the Au sputtering target used for forming an Au film, the use of a cylindrical target is considered as well as a plate-like target. However, in the conventional Au sputtering target, it is difficult to satisfy the uniformity of the film thickness distribution required for an Au film used as an electrode of a quartz oscillator device or the like in any of a plate-like target and a cylindrical target. In particular, in the cylindrical Au sputtering target, it is difficult to improve the uniformity of the film thickness distribution of the Au film derived from the cylindrical processing.

Crystal oscillator devices are used in portable devices, etc., and quartz oscillator devices themselves are also downsized in response to demands for smaller size, lighter weight, thinner, etc. Weight reduction, thickness reduction, etc. are required. For example, the package size of the crystal unit is 5.0 × 3.2 mm (5032 size) to 3.2 × 2.5 mm (3252 size), 2.5 × 2.0 mm (2520 size), Miniaturization is progressing to 0 × 1.6 mm (2016 size) and 1.6 × 1.2 mm (1612 size), and along with this, the crystal oscillator (quartz chip) itself is also miniaturized .

The quartz oscillator device is configured by forming an Au film as an electrode on both sides of a quartz chip (blank) as described above. In the crystal chip, the outer shape is trimmed by etching to round the corners, or the corners are mechanically rounded when pulled out with a press, and the center of gravity is at the center to stabilize the frequency. High smoothness is desirable because the rough surface of the crystal chip adversely affects the frequency characteristics. Also for the electrode formed on the crystal chip, it is desirable that the smoothness be high, that is, the variation in film thickness be small. Since the electrode has a three-dimensional structure having a thickness, when the crystal chip is miniaturized, the influence of the variation in film thickness on the three-dimensional shape becomes larger. Therefore, with the miniaturization of the crystal oscillator device and the like, it is required to further reduce the thickness variation of the Au film applied to the electrode.

Further, in a quartz oscillator having a frequency of 32 kHz used for watch, the variation of the mass of the Au film has a great influence on the frequency characteristics. A shape called a fork type or a tuning fork type is applied to a quartz oscillator having a frequency of 32 kHz. Although the tuning fork type quartz crystal vibrator is suitable for miniaturization, since the mass variation of the Au film affects the frequency characteristics, it is strongly demanded to reduce the mass variation based on the film thickness variation of the Au film. Since tuning fork type quartz oscillator is difficult to adjust the frequency, various devices have been made. For example, with respect to the formation of an Au film, the deposition method is shifted to the sputtering method. After the Au film is formed by sputtering, a part of the Au film is removed by laser beam to adjust the mass, or when forming the Au film by sputtering, it is possible to form a weight for mass adjustment, etc. It has been done. Under such circumstances, if it is possible to reduce mass variations based on thickness variations of the Au film, it is possible to significantly reduce the time required for frequency adjustment. In particular, as the size of the quartz oscillator is reduced, the influence of the film thickness variation is increased, and thus the mass tends to vary. From this point as well, it is required to reduce the variation in film thickness of the Au sputtered film.

Japanese Patent Application Publication No. 2009-512779 JP, 2013-204052, A International Publication No. 2015/111563

An object of the present invention is to provide a gold sputtering target capable of enhancing the uniformity of the film thickness distribution of an Au film.

The gold sputtering target of the present invention is a gold sputtering target comprising a surface to be sputtered and comprising gold and unavoidable impurities, and having an average Vickers hardness of 40 to 60, and an average crystal grain size of 15 to 200 μm. It is characterized in that the {110} plane of gold is preferentially oriented on the surface.

By forming a film by sputtering using the gold sputtering target of the present invention, a gold film excellent in uniformity of film thickness distribution can be obtained with good reproducibility.

Hereinafter, modes for carrying out the present invention will be described. The sputtering target of the embodiment consists of gold (Au) and unavoidable impurities. The unavoidable impurities other than Au contained in the Au sputtering target are not particularly limited. The purity of Au in the sputtering target is set according to the usage of the target and the usage of the film formed using the target, and for example, the Au purity is set to 99.99% or more. By using a sputtering target having an Au purity of 99.99% or more, a high purity Au film can be obtained.

The shape of the Au sputtering target of the embodiment is not particularly limited, and may be any of a plate and a cylinder. As a typical shape of a plate-like sputtering target, for example, a polygonal plate such as a disk or a rectangular plate may be mentioned. In addition to these, for example, a hollow plate is formed by hollowing out a part of a disk or polygon plate, or a part of the surface of a disk or polygon plate is provided with an inclined part, a convex part, a recess or the like. The shape is not particularly limited. The shape of the cylindrical sputtering target is not particularly limited, and a shape or the like corresponding to the sputtering apparatus is applied. As a typical shape of the cylindrical sputtering target, for example, a shape having an outer diameter of 170 to 50 mm, an inner diameter of 140 to 20 mm, and a length of 100 to 3000 mm can be mentioned. The Au sputtering target has a surface to be sputtered (sputtered surface). In the case of a plate-like sputtering target, the surface of the plate is a sputtered surface, and in the case of a cylindrical sputtering target, the surface of a cylinder (cylindrical surface) is a sputtered surface.

The Au sputtering target of the embodiment has a Vickers hardness of 40 or more and 60 or less. By performing sputtering film formation using an Au sputtering target having such Vickers hardness, an Au film excellent in uniformity of film thickness distribution can be formed. That is, that the Vickers hardness of Au sputtering target exceeds 60 HV means that the distortion which arose at the time of manufacture in the sputtering target remains. In such a case, the flying of particles from the target becomes uneven during sputtering, and the uniformity of the film thickness distribution is lost. The Vickers hardness of the Au sputtering target is preferably 55 HV or less. In addition, when heat is applied during sputtering, the hardness and the crystal grain size change, which also reduces the uniformity of particle flight. On the other hand, when the Vickers hardness of the Au sputtering target is less than 40 HV, it is thought that the crystal orientation starts to break up due to the occurrence of crystal grain growth, thereby impairing the uniformity of the film thickness distribution. The Vickers hardness of the Au sputtering target is preferably 45 HV or more.

The Vickers hardness of the Au sputtering target is measured as follows. In the case of a plate-like sputtering target, the measurement point is divided into three in 10 mm intervals on the arbitrary straight line of the sputtering surface (the surface to be sputtered) and in the thickness direction of the first cross section orthogonal to the sputtering surface. 1 area in total (3 places in every 1.5 mm on a straight line in the thickness direction for the sample with a thickness of 5 mm in total), the sputtered surface and the first cross section Area in the thickness direction of the second cross section perpendicular to the direction from the area divided into three parts in total (in the example, 1.5 mm on a straight line in the thickness direction for a 5 mm-thick sample) Every 9 places in total 3 places). The Vickers hardness of each of these measurement points is measured with a test force (press load) of 200 gf. The average value of Vickers hardness in the sputtering surface _{(HV av1),} the average value of Vickers hardness in the first section _{(HV av2),} and the average value of Vickers hardness in the second cross section _{(HV av3),} respectively calculated Do. The average values (HV _av1 , HV _av2 , HV _av3 ) of the sputtered surface, the first cross section, and the second cross section are averaged, and the average value is the average Vickers hardness of the plate-like Au sputtering target as a whole. Value (HV _tav )

In the plate-like Au sputtering target, the ratio (HV _av1 / HV _tav ) of the average value (HV _av1 ) of the Vickers hardness of the sputtering surface to the Vickers hardness (HV _tav ) as the whole target, the first cross section The ratio (HV _av2 / HV _tav ) of the average value (HV _av2 ) of Vickers hardness to the Vickers hardness (HV _tav ) as the target as a whole, and the target as a target of the average value of the Vickers hardness in the second cross section The ratio (HV _{av 3} / HV _tav ) to the Vickers hardness (HV _tav ) is preferably in the range of 0.8 to 1.2, respectively. That is, it is preferable to make the variation in Vickers hardness of the Au sputtering target within ± 20%. As described above, by reducing the variation in Vickers hardness of each part of the Au sputtering target, the flying direction of particles at the time of sputtering can be made more uniform, and the uniformity of the film thickness distribution can be further improved.

When the Au sputtering target is a cylindrical sputtering target, the measurement point is rotated by 90 ° from the first straight line by three points every 10 mm on an arbitrary first straight line parallel to the cylinder axis in the sputtering surface (cylindrical surface) 3 places on every 10 mm on the second straight line, and 1 place from the area divided into 3 in the thickness direction of the cross section orthogonal to the cylinder axis (5 mm in thickness in the example) (3 places in total) at intervals of 1.5 mm on a straight line in the thickness direction with respect to the sample of (a). The Vickers hardness of each of these measurement points is measured with a test force (press load) of 200 gf. The average value of Vickers hardness in the first straight line on the sputtering surface _{(HV av1),} the average value of Vickers hardness in the second straight line _{(HV av2),} and the average value of Vickers hardness in the cross section _{(HV av3} ) Is calculated respectively. The average values (HV _av1 , HV _av2 , HV _av3 ) of the sputtered surface and the cross section are further averaged, and the value is taken as the average value (HV _tav ) of the Vickers hardness of the cylindrical Au sputtering target as a whole.

In the cylindrical Au sputtering target, the ratio (HV _av1 / HV _tav ) of the average value (HV _av1 ) of the first Vickers hardness of the sputtering surface to the Vickers hardness (HV _tav ) as the whole target, the sputtering second average value of Vickers hardness of the surface _{(HV av2)} ratio Vickers hardness for _{(HV tav)} of the target as a whole of _{_(HV} av2 _/ HV _tav), and the average value of Vickers hardness in the cross section _{(HV av3)} It is preferable that the ratio (HV _av3 / HV _tav ) to the Vickers hardness (HV _tav ) as the target as a whole is in the range of 0.8 to 1.2, respectively. That is, it is preferable to make the variation in Vickers hardness of the Au sputtering target within ± 20%. By reducing the variation in Vickers hardness of each part of the cylindrical Au sputtering target, the flying direction of particles at the time of sputtering is further uniformed, and the uniformity of film thickness distribution is further improved. In the cylindrical Au sputtering target, the entire cylindrical surface is sputtered while rotating the cylindrical target. Therefore, the variation in the Vickers hardness at each part of the sputtering surface (cylindrical surface) is reduced, and the uniformity of the film thickness distribution is obtained. Can be improved.

In the Au sputtering target of the embodiment, the average crystal grain size is preferably 15 μm or more and 200 μm or less. By performing sputtering film formation using an Au sputtering target having such an average crystal grain size, the uniformity of the film thickness distribution of the Au film can be further enhanced. That is, when the average crystal grain size of the Au sputtering target is less than 15 μm, the particles may not fly uniformly from the target at the time of sputtering, and the uniformity of the film thickness distribution may be impaired. The average crystal grain size of the Au sputtering target is preferably 30 μm or more. On the other hand, if the average crystal grain size of the Au sputtering target exceeds 200 μm, the flightability of particles during sputtering may be reduced, and the uniformity of the film thickness distribution may be impaired. The average crystal grain size of the Au sputtering target is more preferably 150 μm or less.

The average grain size of the Au sputtering target is measured as follows. When the Au sputtering target is a plate-like sputtering target, the measurement point is a region divided into three in the thickness direction of the first cross section orthogonal to the sputtering surface, at three points of every 10 mm on an arbitrary straight line of the sputtering surface. From a total of three locations (one in every 1.5 mm on a straight line in the thickness direction for the sample with a thickness of 5 mm in each example), the sputtered surface and the first cross section From the area divided by 3 in the thickness direction of the second cross section perpendicular to one another in total three places in each one (in the example, every 1.5 mm on a straight line in the thickness direction for a 5 mm thick sample) A total of nine locations). Take a magnified photo with an optical microscope for each measurement location. The magnification of the photograph is such that the crystal grain size can be easily measured, for example, 50 times or 100 times. Draw straight lines vertically and horizontally so as to pass through the center of the magnified picture, and count the number of grains cut at each straight line. The number of crystal grains at the end of the line segment is 0.5. The length of each straight line in the vertical and horizontal directions is divided by the number of crystal grains to obtain the average grain size in the vertical and horizontal directions, and the average value of these values is taken as the average grain size of one sample.

In this way, the average value of the crystal grain size in the sputter surface _{(AD av1),} the average value of the grain size in the first section _{(AD av2),} and the average value of the grain size of the second section _{(AD av3} ) Is calculated respectively. The average values (AD _av1 , AD _av2 , AD _av3 ) of the crystal grain sizes of the sputtered surface, the first cross section, and the second cross section are further averaged, and the value is obtained as a whole of the plate-like Au sputtering target. Average grain size (AD _tav )

In the plate-like Au sputtering target, the ratio of the average crystal grain size of the target as a whole the average crystal grain size of the sputtering surface of the above-described _{_{(AD av1) (AD tav)}} (AD av1 / AD tav), the first section the average grain size _{(AD av2)} ratio to the average crystal grain size of the target as a whole _{(AD tav)} of _{_(AD} av2 _/ AD _tav), and the average crystal grain size of the second section target as a whole of the _{(AD av3)} The ratio (AD _av3 / AD _tav ) to the average crystal grain size (AD _tav ) is preferably in the range of 0.8 to 1.2, respectively. That is, it is preferable to make the variation of the average crystal grain size of the Au sputtering target within ± 20%. As described above, by reducing the variation of the average crystal grain size of each part of the Au sputtering target, the flying direction of the particles at the time of sputtering is made more uniform, and the uniformity of the film thickness distribution is further improved.

When the Au sputtering target is a cylindrical sputtering target, the measurement point is rotated by 90 ° from the first straight line by three points every 10 mm on an arbitrary first straight line parallel to the cylinder axis in the sputtering surface (cylindrical surface) 3 places on every 10 mm on the second straight line, and 1 place from the area divided into 3 in the thickness direction of the cross section orthogonal to the cylinder axis (5 mm in thickness in the example) (3 places in total) at intervals of 1.5 mm on a straight line in the thickness direction with respect to the sample of (a). Average value of crystal grain size on first straight line of sputtered surface (AD _av1 ), average value of crystal grain size on second straight line (AD _av2 ), and average value of crystal grain size in cross section (AD _av3 ) Are calculated respectively. The average values (AD _{av 1} , AD _{av 2} , AD _{av 3} ) of these sputtered surfaces and cross sections are further averaged, and the value is taken as the average crystal grain size (AD _tav ) as a whole of the cylindrical Au sputtering target.

In cylindrical Au sputtering target, the ratio of the average crystal grain size of the target as a whole of the first average grain size of the sputtering face described above _{_{(AD av1) (AD tav)}} (AD av1 / AD tav), the sputtering surface the average ratio of grain diameter _{(AD tav)} of the target as a whole of the second average grain diameter _{_{_{(AD av2) (AD av2 /}}} AD tav) , and the overall average target grain size _{(AD av3)} in the cross section The ratio of (AD _{av 3} / AD _tav ) to the average crystal grain size (AD _tav ) is preferably in the range of 0.8 to 1.2. That is, it is preferable to make the variation of the average crystal grain size of the Au sputtering target within ± 20%. As described above, by reducing the variation of the average crystal grain size of each part of the cylindrical Au sputtering target, the flying direction of particles at the time of sputtering is further uniformed, and the uniformity of the film thickness distribution is further improved. In the cylindrical Au sputtering target, the entire cylindrical surface is sputtered while rotating the cylindrical target, so that the variation in average crystal grain size in each part of the sputtered surface (cylindrical surface) is reduced to make the film thickness distribution uniform. The sex can be further improved.

In the Au sputtering target of the embodiment, it is preferable that the {110} plane of Au is preferentially oriented on the sputtering surface. Au has a face-centered cubic lattice structure, and among the crystal planes constituting it, the {110} plane is more easily sputtered than other crystal planes. By preferentially orienting such a {110} plane to the sputtered surface, the flying direction of particles at the time of sputtering is stabilized, and therefore the uniformity of the film thickness distribution can be further improved. Here, X-ray diffraction of the sputtered surface of the Au sputtering target is carried out that the sputtered surface is preferentially oriented to the {110} plane, and the following formula (1) of Wilson is obtained from the diffraction intensity ratio of each crystal surface of Au. The orientation index N of each crystal plane is determined from the above, and the case where the orientation index N of the {110} plane is larger than 1 and the largest among the orientation indices N of all crystal planes is shown. The orientation index N of Au {110} plane is more preferably 1.3 or more.

In equation (1), I / I _(hkl) is the diffraction intensity ratio of (hkl) plane in X-ray diffraction, JCPDS · I / I _(hkl) is (hkl) plane in JCPDS (Joint Committee for Powder Diffraction Standards) card diffraction intensities of all crystal planes in the diffraction intensity _{ratio, Σ (I / I (hkl} )) is the sum of the diffraction intensity ratio of the total crystal surface in the X-ray _{diffraction, Σ (JCPDS · I / I} (hkl)) is JCPDS card It is the sum of ratios.

The Au sputtering target of the embodiment is a sputtered Au film based on the combination of the above-mentioned Vickers hardness of 40 or more and 60 or less, the average crystal grain size of 15 μm or more and 200 μm or less and the {110} plane of Au preferentially oriented. This makes it possible to significantly improve the uniformity of the film thickness distribution. That is, by the synergistic action of the Vickers hardness, the average grain size, and the individual effects of the preferred orientation plane of Au mentioned above, the flightability and uniformity of the particles at the time of sputtering, and further the stability of the flight direction of the particles. Improve. For example, when applying an Au sputtered film to an electrode of an electronic device such as a quartz oscillator device whose miniaturization is in progress, the film thickness variation and the mass variation based on it are small, and the film thickness distribution and mass distribution It is possible to provide an Au film excellent in the uniformity of

The manufacturing method of the Au sputtering target of the embodiment mentioned above is not specifically limited. For example, in the case of a plate-like Au sputtering target, it can be manufactured by a manufacturing method combining casting, cutting, forging, and heat treatment of an Au raw material. Also, in the case of a plate-like Au sputtering target, rolling may be applied instead of casting of the Au raw material. In the case of a cylindrical Au sputtering target, it can be manufactured by a manufacturing method combining casting, cutting, pipe processing, and heat treatment of an Au raw material. Examples of pipe processing include extrusion processing such as the Raflo method, drawing processing, forging processing and the like. By controlling the working ratio and heat treatment temperature in each of these working steps, it is possible to obtain the above-mentioned Vickers hardness, average grain size, preferred crystal plane and the like.

In the casting process of the Au raw material, it is melted in a graphite crucible in a vacuum atmosphere or an inert atmosphere, or while blowing an inert gas onto the surface of the molten metal using an air melting furnace, or with the carbon-based solid sealing material. It is preferable to carry out by melting in a graphite crucible while casting and casting in a graphite or cast iron mold. Next, the surface defects on the outer peripheral surface of the cast Au ingot are removed by grinding. The Au purity of the Au ingot is preferably 99.99% or more (4N or more).

When preparing a plate-like Au sputtering target, the Au ingot is forged into a desired plate shape. The forging process of the Au ingot is preferably carried out by hot in the range of 200 to 800 ° C., and it is further carried out so that the working ratio (cross-section reduction rate or thickness reduction rate) becomes 50% to 90%. Is preferred. The forging process may be performed a plurality of times, and heat treatment may be performed on the way. When the forging process is performed a plurality of times, the processing rate is the processing rate as a whole. By setting the processing rate of forging to 50% or more, it is possible to break the cast structure to easily obtain a uniform recrystallized structure and to improve the controllability and uniformity of the hardness and the crystal grain diameter in the subsequent heat treatment process. Can. The Au forging may be subjected to cold rolling, if necessary. The processing rate of the rolling process depends on the processing rate at the time of forging, but is preferably 50% to 90%. Furthermore, in place of the forging process, a rolling process may be applied to the process of processing the Au ingot. The rolling process of the Au ingot is preferably performed in the range of 200 to 800 ° C. in the same manner as the forging process, and the working ratio (the reduction in area or the reduction in thickness) is in the range of 50 to 90%. It is preferable to carry out so that

In the case of producing a cylindrical Au sputtering target, an Au billet formed into a cylindrical shape is processed into a pipe shape by extrusion, drawing, forging, or the like such as the Raflo method. In the case of applying extrusion processing such as the Raflo method, the extrusion processing is preferably performed cold, and the outer diameter and thickness of the pipe are determined by the shape of the die (inner diameter etc.) and the shape of the mandrel (outside diameter etc.) Control. At this time, it is preferable to adjust the extrusion ratio (outside diameter of billet / outside diameter of pipe) to be 1.5 or more and 3.0 or less. By setting the extrusion ratio to 1.5 or more, it is possible to break the cast structure to easily obtain a uniform recrystallized structure and to improve the controllability and uniformity of hardness in the subsequent heat treatment step. However, when the extrusion ratio exceeds 3.0, the internal strain becomes too large, and cracks and wrinkles easily occur.

When drawing processing is applied, it is preferable to draw out an Au base tube produced by extrusion processing or hollowing processing by cold drawing and process it into a pipe shape of a desired shape, and also the shape of the die (inner diameter etc.) and plug The outer diameter and thickness of the pipe are controlled by the shape (outside diameter etc.). Under the present circumstances, it is preferable to adjust the processing rate per time to 2% or more and 5% or less. The drawing process may be repeated several times, and in such a case, it is preferable to adjust the total processing rate to 50% or more and 90% or less. By setting the total processing ratio to 50% or more, it is possible to break the cast structure to easily obtain a uniform recrystallized structure and to improve the controllability and uniformity of hardness in the subsequent heat treatment step.

In the case of applying forging, it is preferable to hot forge the Au base tube produced by extrusion or hollowing at a temperature in the range of 200 to 800 ° C. and process it into a desired pipe shape, and also processing at the time of forging The rate controls the outer diameter and thickness of the pipe. The forging step is preferably performed with the processing rate adjusted to 30% or more and 80% or less. By setting the processing rate to 30% or more, it is possible to break the cast structure to easily obtain a uniform recrystallized structure and to improve the controllability and uniformity of hardness in the subsequent heat treatment step. However, if the processing rate exceeds 80%, the internal strain becomes too large, and cracks and wrinkles are easily generated.

Next, the plate-like target material produced in the forging process or the rolling process, and the pipe-like target material produced in the pipe processing process are heated, for example, in the atmosphere or in an inert gas atmosphere at a temperature of 200 ° C. to 500 ° C. The metal structure of the target material is recrystallized by heat treatment at. By such heat treatment, an Au sputtering target having a Vickers hardness of 40 or more and 60 or less can be obtained. Furthermore, it is possible to obtain an Au sputtering target having an average crystal grain size of 15 μm or more and 200 μm or less, or an Au sputtering target in which the sputtering surface is preferentially oriented to the {110} plane. The heat treatment step may be performed multiple times. After the heat treatment step, a step of adjusting the shape of the sputtering target by cutting or the like may be performed as necessary.

When the heat treatment temperature is less than 200 ° C., the internal strain generated at the time of processing can not be sufficiently removed, and the Vickers hardness may exceed 60. Furthermore, since the metal structure of the target material can not be sufficiently recrystallized, the average crystal grain size may be less than 15 μm, or the sputtered surface may not be preferentially oriented to the {110} plane. On the other hand, when the heat treatment temperature exceeds 500 ° C., the Vickers hardness may be less than 40. Furthermore, the recrystallized structure may grow too much, and the average crystal grain size may exceed 200 μm, or the sputtered plane may be preferentially oriented to a crystal plane other than the {110} plane. The holding time (heat treatment time) according to the heat treatment temperature is preferably, for example, 10 minutes or more and 120 minutes or less. If the heat treatment time is too short, there is a possibility that the removal of the strain is insufficient or the metal structure can not be sufficiently recrystallized. On the other hand, if the heat treatment time is too long, the Vickers hardness may be too low, or the average grain size may be too large.

As described above, the Vickers hardness is 40 or more and 60 or less, and the variation in Vickers hardness is controlled by controlling the working ratio in the step of processing the Au ingot into a plate or cylindrical shape and the temperature of the recrystallization heat treatment step. Can obtain a small Au sputtering target. Furthermore, it is possible to obtain an Au sputtering target having an average crystal grain size of 15 μm to 200 μm and a small variation in the average crystal grain size, or an Au sputtering target in which the sputtered surface is preferentially oriented to the {110} plane. By forming an Au film by using such an Au sputtering target, it is possible to obtain an Au film which satisfies the uniformity of the film thickness distribution required for an electrode of, for example, a quartz oscillator device. The Au sputtering target of the present invention can be used not only for forming an electrode film (Au film) of a quartz oscillator device, but also for forming an Au film applied to various electronic components.

Next, specific examples of the present invention and the evaluation results thereof will be described.

Example 1
First, an Au block was inserted into a graphite crucible and melted. Au molten metal was cast into a graphite mold to prepare an Au ingot. By grinding and removing the surface of the Au ingot, an Au billet (purity 99.99%) having a width of 190 mm, a length of 270 mm and a thickness of 50 mm was produced. Then, the Au billet was hot forged at a temperature of 800 ° C. to form an Au target material having a width of 70 mm, a length of 200 mm, and a thickness of 45 mm. The processing rate during forging was 80% in all three axial directions. The forged Au target material was heat treated at a temperature of 500 ° C. for 30 minutes. The heat-treated Au target material was ground to prepare a disk-shaped Au sputtering target having a diameter of 152.4 mm and a thickness of 5 mm. Two Au sputtering targets were prepared for measuring the characteristics of each part and measuring the film thickness characteristics. The same applies to the following examples and comparative examples.

The Vickers hardness of the obtained Au sputtering target was measured in accordance with the measurement method of the plate-like sputtering target described above. As a result of measuring the Vickers hardness of each measurement location mentioned above by the test force (press load) of _{200 gf,} the average value (HV _av1 ) of the Vickers hardness of a sputtering surface is 50.5, and the Vickers hardness of the 1st section the average value _{(HV av2)} is 52.1, the mean value of Vickers hardness of the second section _{(HV av3)} is 51.6, the average value of these values (Vickers hardness of the target as a whole _{(HV tav)} ) Was 51.4. The ratio of each part of the Vickers hardness for the Vickers hardness of the target as a whole _{_{_{(HV tav) (HV av1,}}} HV av2, HV av3) _is, _HV av1 _/ HV _tav is _0.98, _HV av2 _/ HV _tav 1.01 , HV _av3 / HV _tav was 1.00.

Furthermore, the average crystal grain size of the Au sputtering target was measured according to the measurement method of the plate-like sputtering target described above. As a result, the average grain size (AD _tav ) of the entire target was 34.2 μm. In addition, the sputtered surface of the Au sputtering target was subjected to X-ray diffraction, and the crystal plane preferentially oriented was evaluated according to the method described above. As a result, it was confirmed that the {110} plane of Au is preferentially oriented on the sputtered surface. When the orientation index N of the {110} plane was determined according to the method described above, the orientation index N of the {110} plane was 1.32. The characteristics were evaluated by using such an Au sputtering target in a film forming process described later.

(Examples 2 to 5, Comparative Examples 1 to 2)
An Au target material was produced by forging in the same manner as in Example 1 except that the working ratio shown in Table 1 was applied using an Au billet produced in the same manner as in Example 1. Next, heat treatment was performed on the forged Au target material under the conditions shown in Table 1. After that, the Au target material after the heat treatment was ground to produce an Au sputtering target having the same shape as that of Example 1. The Vickers hardness, average grain size, preferred orientation plane of sputtered surface, and orientation index N of {110} plane of these Au sputtering targets were measured and evaluated in the same manner as in Example 1. The measurement results are shown in Table 2. The characteristics were evaluated by using such an Au sputtering target in a film forming process described later.

The Au sputtering targets according to Examples 1 to 5 and Comparative Examples 1 and 2 described above are attached to a single-plate sputtering apparatus, and the inside of the apparatus is evacuated to 1 × 10 ⁻³ Pa or less, and then Ar gas pressure: 0.4 Pa, Sputtering was performed under the conditions of input power: DC 100 W, target-substrate distance: 40 mm, and sputtering time: 5 minutes to form an Au film on a 6-inch Si substrate (wafer). The film thickness distribution of the obtained Au film was evaluated as follows. A substrate on which an Au film is formed is attached to a fluorescent X-ray film thickness meter, measurement time: 60 seconds, repeated measurement: 10 times, measurement start point: substrate edge, measurement point interval: 5 mm, The film thickness was measured. The film thickness measurement axes were four axes, that is, two vertical and horizontal axes passing through the center of the substrate, and two vertical and horizontal axes passing through the center of the substrate in a state rotated 45 degrees therefrom. After measurement, the 10-point average film thickness of each measurement point was calculated, the standard deviation of the measurement values at the same measurement position of 4 axes was calculated, and the average value of the standard deviation of all measurement positions was calculated. This value is shown in Table 3 as the standard deviation σ of the film thickness. Next, the resistance value of the Au film was measured by the four probe method, and the standard deviation σ of the resistance value was determined in the same manner as the film thickness. The results are shown in Table 3 as the standard deviation σ of the resistance value of the Au film.

As apparent from Table 3, in each of the Au sputtering targets of Examples 1 to 5, it is understood that the Vickers hardness is in the range of 40 to 60, and the variation in Vickers hardness of each part is also small. It is understood that the average grain size is in the range of 15 to 200 μm, the {110} plane is preferentially oriented on the sputtered surface, and the orientation index N of the {110} plane is larger than 1. An Au film formed by sputtering using an Au sputtering target in which such Vickers hardness, average grain size, and preferred orientation plane of the sputtering surface are combined is excellent in uniformity of film thickness distribution and resistance value. It can be seen that the uniformity is also excellent.

(Examples 6 to 10)
An Au target material was produced by forging in the same manner as in Example 1 except that the working ratio shown in Table 4 was applied using an Au billet produced in the same manner as in Example 1. Next, the forged Au target material was heat-treated under the conditions shown in Table 4. After that, the Au target material after the heat treatment was ground to produce an Au sputtering target having the same shape as that of Example 1.

The Vickers hardness of the obtained Au sputtering target was measured in the same manner as in Example 1. Furthermore, the average crystal grain size of the Au sputtering target was measured according to the measurement method of the plate-like sputtering target described above. As a measurement result, the average grain size (AD _{av 1} , AD _{av 2} , AD _{av 3} ) of each of the sputtered surface, the first cross section, and the second cross section, the average value of these respective values (average crystal grain size as the whole target The ratio of the average grain size (AD _av1 , AD _av2 , AD _av3 ) of each _{portion to} (AD _tav )) and the average grain size (AD _tav ) of the whole target is shown in Table 5. Furthermore, the sputtered surface of the Au sputtering target was subjected to X-ray diffraction, and the preferentially oriented crystal plane was evaluated according to the method described above. The orientation index N of the {110} plane was determined according to the method described above. The results are shown in Table 5. Using such an Au sputtering target, the film forming process was performed in the same manner as in Example 1, and the standard deviation σ of the film thickness of the Au film and the standard deviation σ of the resistance value were obtained. The results are shown in Table 6.

(Examples 11 to 19, Comparative examples 3 to 4)
First, an Au block was inserted into a graphite crucible and melted. Au molten metal was cast into a graphite mold to prepare an Au ingot. By grinding and removing the surface of the Au ingot, an Au billet (purity 99.99%) having a width of 200 mm, a length of 300 mm, and a thickness of 45 mm was produced. Subsequently, the Au billet was hot-rolled at a temperature of 800 ° C. to obtain an Au target material having a width of 70 mm, a length of 200 mm, and a thickness of 45 mm. The processing rate at the time of rolling was 80% as the reduction rate of thickness. The rolled Au target material was heat treated under the conditions shown in Table 7. The heat-treated Au target material was ground to prepare a disk-shaped Au sputtering target having a diameter of 152.4 mm and a thickness of 5 mm.

About the obtained Au sputtering target, it carried out similarly to Example 1 and measured the average value ( _HVtav ) of the Vickers hardness as the whole target, and the average grain size ( _ADtav ) as the whole target. Furthermore, the crystal plane preferentially oriented on the sputtered surface of the Au sputtering target was evaluated in the same manner as in Example 1, and the orientation index N of the {110} plane was determined in the same manner as in Example 1. The results are shown in Table 8. Using such an Au sputtering target, the film forming process was performed in the same manner as in Example 1, and the standard deviation σ of the film thickness of the Au film and the standard deviation σ of the resistance value were obtained. The results are shown in Table 9.

Example 20
First, an Au block was inserted into a graphite crucible and melted. Au molten metal was cast into a graphite mold to prepare an Au ingot. The surface of the Au ingot was ground and removed, and hollowed with an inner diameter of 50 mm to produce a cylindrical Au billet (purity 99.99%) having an outer diameter of 100 mm, an inner diameter of 50 mm, and a length of 200 mm. Next, with the core inserted in the hollow portion of the cylindrical Au billet, the core is heated to a temperature of 800 ° C. and hot forged, and a pipe-shaped Au target having an outer diameter of 80 mm, an inner diameter of 50 mm and a length of 400 mm or more It was a material. The processing rate at the time of forging was 35% as the reduction rate of thickness. The forged pipe-like Au target material was heat-treated at a temperature of 500 ° C. for 30 minutes. By grinding the Au target material after the heat treatment, a cylindrical Au sputtering target having an outer diameter of 70 mm, an inner diameter of 65 mm, and a length of 350 mm was produced.

The Vickers hardness of the obtained Au sputtering target was measured according to the measuring method of the cylindrical sputtering target mentioned above. The average Vickers hardness (HV _av1 ) on the first straight line of the sputter surface as a result of measuring the Vickers hardness of each measurement point with a test force (press load) of _{200 gf} is 50.6, the second of the sputter surface The average value (HV _av2 ) of the Vickers hardness on the straight line of 2 is 50.4, the average value (HV _av3 ) of the Vickers hardness at the cross section is 52.0, and the average value of these respective values (Vickers hardness as the whole target (HV _tav )) was 51.0. The ratio of the Vickers hardness (HV _av1 , HV _av2 , HV _av3 ) of each part to the Vickers hardness (HV _tav ) as the entire target is HV _av1 / HV _tav 0.99, HV _av2 / HV _tav 0. 99, _HVav3 / _HVtav was 1.02.

Furthermore, the average crystal grain size of the Au sputtering target was measured according to the measurement method of the cylindrical sputtering target described above. As a result, the average grain size (AD _tav ) of the entire target was 38.1 μm. In addition, the sputtered surface of the Au sputtering target was subjected to X-ray diffraction, and the crystal plane preferentially oriented was evaluated according to the method described above. As a result, it was confirmed that the {110} plane of Au is preferentially oriented on the sputtered surface. When the orientation index N of the {110} plane was determined according to the method described above, the orientation index N of the {110} plane was 1.31. The characteristics were evaluated by using such a cylindrical Au sputtering target in a film forming process described later.

(Examples 21 to 24 and Comparative Examples 5 to 6)
A cylindrical Au target material was produced in the same manner as in Example 20 except that the working rates shown in Table 10 were applied using an Au billet produced in the same manner as in Example 20. Next, heat treatment was performed on the forged Au target material under the conditions shown in Table 10. Thereafter, the Au target material after the heat treatment was ground to produce an Au sputtering target having the same shape as that of Example 20. The Vickers hardness and the average crystal grain size (AD _tav ) of these Au sputtering targets were measured in the same manner as in Example 20. Furthermore, the crystal plane preferentially oriented to the sputtered surface of the Au sputtering target was evaluated in the same manner as in Example 20, and the orientation index N of the {110} plane was determined in the same manner as in Example 20. The results are shown in Table 11. The characteristics were evaluated by using such a cylindrical Au sputtering target in a film forming process described later.

The Au sputtering targets according to Examples 20 to 24 and Comparative Examples 5 to 6 described above are attached to a cylindrical sputtering apparatus, and the inside of the apparatus is evacuated to 1 × 10 ^-3 Pa or less, and then Ar gas pressure: 0.4 Pa, Sputtering was performed under the conditions of input power: DC 100 W, target-substrate distance: 40 mm, and sputtering time: 5 minutes to form an Au film on a 6-inch Si substrate (wafer). The film thickness distribution of the obtained Au film was measured according to the method described above, and the standard deviation σ of the film thickness of the Au film was determined. Further, the standard deviation σ of the resistance value of the Au film was determined according to the method described above. The results are shown in Table 12.

As apparent from Table 12, in each of the Au sputtering targets of Examples 20 to 24, it is understood that the Vickers hardness is in the range of 40 to 60, and the variation in Vickers hardness of each part is also small. It is understood that the average grain size is in the range of 15 to 200 μm, the {110} plane is preferentially oriented on the sputtered surface, and the orientation index N of the {110} plane is larger than 1. An Au film formed by sputtering using an Au sputtering target in which such Vickers hardness, average grain size, and preferred orientation plane of the sputtering surface are combined is excellent in uniformity of film thickness distribution and resistance value. It can be seen that the uniformity is also excellent.

(Examples 25 to 29)
A cylindrical Au target material was produced in the same manner as in Example 20 except that the working ratio shown in Table 13 was applied using an Au billet produced in the same manner as in Example 20. Next, the forged Au target material was heat-treated under the conditions shown in Table 13. Thereafter, the Au target material after the heat treatment was ground to produce an Au sputtering target having the same shape as that of Example 20.

The Vickers hardness of the obtained Au sputtering target was measured in the same manner as in Example 20. Furthermore, the average crystal grain size of the Au sputtering target was measured according to the measurement method of the cylindrical sputtering target described above. As a measurement result, the average value (AD _{av 1} , AD _{av 2} , AD _{av 3} ) of the crystal grain size of each of the first sputtered surface, the second sputtered surface, and the cross section, and the average value of these respective values (average as a whole target) the ratio of the crystal grain size _{(AD tav)),} and the average crystal grain size of each section to the average crystal grain size of the target as a whole _{_{_{(AD tav) (AD av1,}}} AD av2, AD av3), shown in Table 14. Furthermore, the sputtered surface of the Au sputtering target was subjected to X-ray diffraction, and the crystal plane preferentially oriented was evaluated according to the method described above, and the orientation index N of the {110} plane was determined. The results are shown in Table 14. Using such an Au sputtering target, the film forming step was carried out in the same manner as in Example 20, and the standard deviation σ of the film thickness of the Au film and the standard deviation σ of the resistance value were measured. The results are shown in Table 15.

The Au sputtering target of the present invention is useful for forming an Au film used for various applications. Further, by performing sputtering using the Au sputtering target of the present invention, it is possible to obtain an Au film excellent in uniformity of film thickness distribution and resistance value. Therefore, the characteristics of the Au film used for various applications can be enhanced.

Claims

A gold sputtering target comprising gold and unavoidable impurities and having a surface to be sputtered,
The average value of Vickers hardness is 40 or more and 60 or less,
An average crystal grain size of 15 μm to 200 μm,
A gold sputtering target, in which the {110} plane of gold is preferentially oriented on the surface.
When the orientation index N of each crystal plane is determined from the diffraction intensity ratio of each crystal plane of gold by X-ray diffraction of the surface, the orientation index N of the {110} plane of gold is 1 The gold sputtering target according to claim 1, which is the largest and the largest among all the crystallographic orientation indices N.

In the equation (1), I / I (hkl) is a diffraction intensity ratio of (hkl) plane in X-ray diffraction, JCPDS · I / I (hkl) is a diffraction intensity ratio of (hkl) plane in JCPDS card, Σ (I / I (hkl) is the sum of the diffraction intensity ratio of all crystal planes in X-ray diffraction, and ((JCPDS · I / I (hkl) ) is the sum of the diffraction intensity ratio of all crystal planes in the JCPDS card.
The gold sputtering target according to claim 1 or 2, wherein the variation of the Vickers hardness as the entire sputtering target is within ± 20%.
The gold sputtering target according to any one of claims 1 to 3, wherein the variation of the average crystal grain size as a whole of the sputtering target is within ± 20%.
The gold sputtering target according to any one of claims 1 to 4, wherein the gold purity of the sputtering target is 99.99% or more.
The gold sputtering target according to any one of claims 1 to 5, which has a plate shape.
The gold sputtering target according to any one of claims 1 to 5, which has a cylindrical shape.